Production of vinylidene-terminated and sulfide-terminated telechelic polyolefins via quenching with disulfides

Abstract

Provided herein are methods for preparing vinylidene-terminated polyolefins. Further, provided herein are novel sulfide-terminated polyolefins of the formula: wherein R 1 is a polyolefin group and R 2 is hydrocarbyl; and methods for producing the same.

What is claimed: 
     
       1. A method for preparing a compound of formula II or III or mixtures thereof: 
       
         
           
           
               
               
           
         
         wherein R 1  is a polyolefin group;
 R A  and R B  are each, independently, alkyl, aryl, aralkyl, alkaryl, 
 
       
       
         
           
           
               
               
           
         
          wherein m is 1-3; n is 1-3; p is 1-3;
 X is halo or a pseudohalide; 
 R x  is alkyl or aryl; 
 R 3  is tert-butyl; and 
 R 4  and R 5  are each, independently, alkyl, aryl, aralkyl, or alkaryl; 
 
       
       comprising:
 (a) ionizing a polyolefin in the presence of a Lewis acid or mixture of Lewis acids to form an ionized polyolefin; 
 (b) reacting the ionized polyolefin from step (a) with one or more compounds of formula IV:
   R A —S—S—R B    IV
 
 
  to form an intermediate; and 
 (c) reacting the intermediate of step (b) with one or more alcohols, amines, or thiols. 
 
     
     
       2. The method of  claim 1 , wherein R 1  is a polyisobutylene group. 
     
     
       3. The method of  claim 1 , wherein R A  and R B  are each, independently, alkyl, aryl, alkaryl, aralkyl, 
       
         
           
           
               
               
           
         
         wherein n is 1-3; p is 1-3;
 X is halo or a pseudohalide; 
 
         R 3  is tert-butyl; and 
         R 4  and R 5  are each, independently, aryl or alkyl; 
         and R x  is alkyl. 
       
     
     
       4. The method of  claim 1 , wherein R A  and R B  are the same. 
     
     
       5. The method of  claim 4 , wherein R A  and R B  are methyl, ethyl, isopropyl, or tolyl. 
     
     
       6. The method of  claim 4 , wherein R A  and R B  are 
       
         
           
           
               
               
           
         
       
     
     
       7. The method of  claim 6 , wherein n is 2. 
     
     
       8. The method of  claim 4 , wherein R A  and R B  are 
       
         
           
           
               
               
           
         
       
     
     
       9. The method of  claim 8 , wherein n is 2. 
     
     
       10. The method of  claim 8 , wherein X is Cl or Br. 
     
     
       11. The method of  claim 4 , wherein R A  and R B  are 
       
         
           
           
               
               
           
         
       
     
     
       12. The method of  claim 11 , wherein p is 2. 
     
     
       13. The method of  claim 11 , wherein R 4  and R 5  are phenyl or methyl. 
     
     
       14. The method of  claim 1 , wherein the intermediate of step (b) is reacted with one or more alcohols. 
     
     
       15. The method of  claim 14 , where the one or more alcohols are
   R—OH;
 
 
       wherein R is alkyl of 1-8 carbons. 
     
     
       16. The method of  claim 15 , wherein the one or more alcohols are one or more of methanol or isopropanol. 
     
     
       17. The method of  claim 16  wherein the one or more alcohols are methanol. 
     
     
       18. The method of  claim 1 , where the intermediate of step (b) is reacted with one or more amines. 
     
     
       19. The method of  claim 18 , wherein the one or more amines are of the formula: 
       
         
           
           
               
               
           
         
         wherein R 6  is alkyl; and 
         R 7  and R 8  are each, independently, hydrogen or alkyl of 1-8 carbons. 
       
     
     
       20. The method of  claim 19 , wherein the one or more amines are one or more of n-butylamine, 2-ethylhexylamine, tert-amylamine, triethylamine, or dibutylamine. 
     
     
       21. The method of  claim 1 , wherein the intermediate of step (b) is reacted with one or more thiols. 
     
     
       22. The method of  claim 21 , wherein the one or more thiols are of the formula
   R C1 —SH;
 
 
       wherein R C1  is alkyl of 1-6 carbons. 
     
     
       23. The method of  claim 22 , wherein the one or more thiols are one or more of ethanethiol or n-propanethiol. 
     
     
       24. The method of  claim 1 , wherein the compound of formula II or III or mixtures thereof is at least 20 mole percent of all products formed. 
     
     
       25. The method of  claim 1 , wherein the compound of formula II or III or mixtures thereof is at least 40 mole percent of all products formed. 
     
     
       26. The method of  claim 1 , wherein the ionized polyolefin is formed by adding a Lewis acid to a tert-halide terminated polyolefin or adding a Lewis acid and a proton source to a preformed polyolefin. 
     
     
       27. The method of  claim 1 , wherein the ionized polyolefin is a quasiliving carbocationic polyolefin and the method is performed under quasiliving carbocationic polymerization conditions. 
     
     
       28. The method of  claim 27 , wherein the quasiliving carbocationic polyolefin is prepared by adding a Lewis acid and a monomer to an initiator in the presence of an electron donor, common ion salt, or common ion salt precursor. 
     
     
       29. The method of  claim 28 , wherein the initiator is 2-chloro-2,4,4-trimethylpentane, 1,3-di(2-chloro-2-propyl)-5-tert-butylbenzene, or dicumyl chloride. 
     
     
       30. The method of  claim 28 , wherein the monomer is isobutylene or styrene. 
     
     
       31. The method of  claim 28 , wherein the electron donor is pyridine or a pyridine derivative. 
     
     
       32. The method of  claim 31 , wherein the electron donor is 2,6-dimethylpyridine, 2,4-dimethylpyridine, or 2,6-di-tert-butylpyridine. 
     
     
       33. The method of  claim 28 , wherein the common ion salt precursor is tetrabutylammonium chloride or tetrabutylammonium iodide. 
     
     
       34. The method of  claim 1 , wherein the Lewis acid is a titanium tetrahalide, a boron trihalide, aluminum trihalide, tin tetrahalide, zinc chloride, or ethyl aluminum dichloride, or mixtures thereof. 
     
     
       35. The method of  claim 34 , wherein the Lewis acid is titanium tetrachloride. 
     
     
       36. The method of  claim 1 , wherein a mixture of Lewis acids is used. 
     
     
       37. The method of  claim 36 , wherein the mixture of Lewis acids is a mixture of an aluminum (III) halide and trialkyl aluminum compound. 
     
     
       38. The method of  claim 1 , wherein a diluent is used. 
     
     
       39. The method of  claim 38 , wherein the diluent is an alkane or alkyl halide or mixtures thereof. 
     
     
       40. The method of  claim 1 , wherein the method is performed at a temperature from about −120° C. to about 0° C. 
     
     
       41. The method of  claim 40 , wherein the temperature is from about -70° C. to about −40° C. 
     
     
       42. The method of  claim 1 , wherein the Lewis acid or mixture of Lewis acids are present at a molar concentration of from about 0.5 to about 20 times chain-end molar concentration. 
     
     
       43. The method of  claim 28 , wherein the one or more compounds of formula IV is added after at least 85% of the monomer is polymerized.